Splitting-off of hydrogen halide from halogenated hydrocarbons



Patented June 19, 1945 srrrr'rnva-or'r or nrnaoasn mums mom nanoceuaran nrnaocaanoms Martin Richmond, and Dereh Harold Richard Barton, London, England,

asaignors to The Distillers Company Limited, Edinburgh, Scotland, at British company No Drawing. Application December 31, 1942, Se-

gall-No. 470,840. In Great Britain August 11 Claims.

This invention is for improvements in or relating to the splitting-off or hydrogen chloride :Irom chlorinated hydrocarbons.

In the splitting-cit of hydrogen chloride from v chlorinated hydrocarbons, many catalysts, particularly metal chlorides, have been proposed and are in fact in use, the vapour of the compound being passed over the catalyst at an elevated temperature. For large scale commercial use these processes present the same disadvantages as other heterogeneous catalytic reactions principally the low heat conductivity of the catalyst and its restricted useful life.

, We have found, that the dissociation of many aliphatic chlorinated hydrocarbons can be effected in an unexpectedly simple and easy way' and according to the invention there is provided a process for splitting-oil. hydrogen chloride from an aliphatic chlorinated hydrocarbon containing 2 or 3 carbon atoms in the molecule and containing the group CHClCHClwhich comprises in the vapour phase carrying out the reaction at an elevated temperature in the presence of a small amount of chlorine or bromine or a compound which yields chlorine or bromine at an elevated temperature, such as for example suliuryl chloride, thionyl chloride, hexachloroethane and the like. In some cases the temperature at which hydrogen chloride is split oiI is reduced by several hundred degrees centigrade by the process of the invention as compared with dichloride was condensed out of the issuing gases,

which were then washed with water to remove hydrogen chloride, dried with calcium chloride, and the vinyl chloride which is the desired end product was then condensed at low temperature. The excess ethylene dichloride was gently refluxed to prevent vinyl chloride becoming or rethermal decomposition processes in which no halogen is used as catalyst. The process does not appear to be a true catalysis, for the halogen, or the greater part thereof disappears during the reaction. It is probable that the halogen acts by starting chain-reactions. In carrying out the process of the present invention, care has to be taken that the halogen and/or the halogen-yielding compounds are not destroyed before the temperature of reaction is reached. In some cases therefore they must be added to the vapour immediately before the entrance of the vapour into the reaction chamber. .In other cases, the halogen or halogen-yielding compound can simply be dissolvedin the chlorinated hydrocarbon.

The following examples illustrate the invention:

Example I.Ethylene dichloride was mixed with 56% by weight of chlorine. 38 gr. per hour were dropped in a uniform stream into the upper end of a tube of a heat resistant glass of 11 mm. diameter, 800 mm. length, somewhat inclined and heated over a length of 600 mm. to the temperature indicated below. The unreacted ethylene maining dissolved therein. At 300 C. about 30% and at 350 C. about 50% by weight 0! the ethylene dichloride was converted into vinyl chloride, whilst at 370 C. about by weight 01 vinyl chloride was obtained. Without the addition of chlorine the conversion at 400 C. was only 2% by weight and even at 500 C. not more than 30% by weight could be obtained. The quantity of the chlorine added could be lowered to 0.05% by weight without much decrease in the yield. No by-products other than a trace of acetylene were formed. Bromine also proved eflective in promoting the reaction.

Example II.Symmetrical tetrachloroethane was mixed with by weight 01 chlorine and 30 gr. per hour 01' this mixture were dropped into a tube similar to that used in Example I. The products thus obtained were introduced into cooled water and condensed therein. At 300 C. 50% by weight were transformed into trichloroethylene, at 350 C. and at 400 C. by weight was obtained. No by-products were produced. Without the addition of chlorine the conversion was at 300 0. ml and at 400 C. only 65% by weight.

Example III.-l-1-2-trichloroethane, containing 0.5% by weight chlorine were treated in the same way as described in Example I. With an input of 30 gr. per hour the conversion was: at 350 C. 45% and at 400 C. 85% by weight. Without chlorine at 350 C. 1.5% and at 400 C. 4% by weight only were obtained. The product was a mixture of the asymmetrical and the symmetrical dichloroethylenes, in which the asymmetric compound largely predominates. No other products were formed.

Example IV.Ethylene dichloride was mixed with 0.5% by weight of suliuryl chloride and heated in the apparatus described in Example I. At 350 C. a 50% conversion was obtained, 1. e. the same conversion rate as with chlorine. The input was 40 gr. per hour.

Example V.--Ethylene dichloride mixed with 0.5% by weight of hexachloroethane, gave with an input c gr. per hour at 350 C. 3.8% at 400 C. 12% and at 450 C. 46% by weight of vinyl chloride.

Example VI.Propylene dichloride vapour was passed through the tube at the rate of 26 gms. per hour, 3% by weight of chlorine being introduced simultaneously. At 380 C. 16% by weight of the propylene dichloride was converted into a mixture of monochlorpropylenes, 'whilst at 430 C. 21% were converted. In the absence of chicrine, no conversion was obtained at 380 0., and

only 1% of the propylene verted at 430 C. V

The velocity of reaction is much influenced dichloride was conby small quantities of impuritiea'as is known for many other chain reactions; the yieldobtained from different batches of raw materials may therefore vary somewhat under identical conditions or reaction. However, in every case,

the addition of chlorine or bromine had a benealkali or with both in succession followed by washing with water. The ethylene dichloride used in Example I was obtained by purifying a commercial product made from alcohol via ethylene. The crude product, mixed with 0.5% by weight of chloride, gave at 500 C. a 16% by weight conversion, whilst without the addition of chlorine the yield was only 4%. The efiect of the chlorine on the yield is evident here, but the purified material reacts mor rapidly at a temperature which is lower by 200 C. Similarly,

with symmetrical tetrachloroethane the commercial product gives a 50% by weight conversion at 350 C. with chlorine, whilst without chlorine no reaction at all takes place at this temperature. As shown in Example 11 the pure product gives this yield at 300 C.

It has been found that small amounts of oxygen (as little as 3 mols. per cent of the chlorine or bromine), which may be absorbed from the air by the reaction materials or be added thereto, exert a beneficial influence on the reaction, leading to somewhat higher conversion figures. The materials used in Examples I to V1 probably contain such traces of oxygen as no precautions were taken rigidly to exclude oxygen from the reaction.

The following further examples illustrate the eifect of oxygen on the reaction:

Example VII.-54 gms. per hour of pure ethylene dichloride, previously freed from dissolved oxygen by boiling, were assed, in vapour form, through a tube of heat resistant glass of 11 mm. internal diameter which was heated to 350 CI over a length of 600 mm. Simultaneously 0.5% (by weight) of chlorine was introduced into the tube. The latter was taken from a cylinder with a low content of chlorine, so that little or no oxygen would be present in the chlorine. The conversion of ethylene dichloride into vinyl chloride varied between 17% and of the ethylene chloride introduced. If new 15 ccs. of air (equivalent to 3 cos. of oxygen) were added to the chlorine per hour, the conversion of ethylene dichloride increased to 36 to 48%. By increasing the amount of oxygen added to ccs. per hour,

morethan50% oftheethylenedlchloridewas converted.

' Example VIIL32 ms r symmetrical tetrhchlorethane, freed from air by boiling, were with 1% by weight of chlorine. 11% 0f the tetrachlorethane were decomposed at 350 C. to trichlorethylene. By adding 6 cos. of oxygen per hour, the decomposition increased to 50%.

Packing the reaction tube with glass scraps decreases the reaction velocity as V unsaturated hydrocamons by the emitting-on.

of one molecule of hydrogen chloride from a molecule of a chlorinated hydrocarbon containingatleast2andnotmorethan3carbmattms in the molecule and including the grouping which comprises carrying out the reaction in the vapour phase at an elevated temperature in the presence of a small amount of a member of the group consisting of chlorine, bromine, compounds which yield chlorine at an elevated temperature. and compounds which yield bromine at an elevated temperature.

2. Aprocess accordingtoclaim 1 whereinthe said member is added to the chlorinated hydrocarbon vapour immediately before entry of the reactants into the reaction zone.

3. Aprocess accordingtoclaim 1 whereinthe halogen is present in an amount of about 0.512) 3% by weight of the chlorinated hydrocarbon.

4. Aprocessaccordingtoclaimlwhereinthe halogen is added to the chlorinated hydrocarbon vapour immediately before entry of the reactants into the reaction zone and in an amount of about 0.5 to 3% by weight of the chlorinated hydrocarbon.

5. AprocessaccordingtoclaimI whereinthe chlorinated hydrocarbon is purified prior to the reaction.

6. A process according to claim 1 wherein a small amount of oxygen is added to the reaction 7. A process for the manufacture of chlorinated unsaturated hydrocarbons by the splitting-oil of one molecule of hydrogen chloride from a moleclue of a chlorinated hydrocarbon atleast2andnotmorethan3carbdnatomsin the molecule and the grouping CHC'l CHCl which comprises carrying out the reaction in the vapour phase at an elevated temperamre in the presence of a small amount oi a member of the group consisting of'chlorine, bromine, compounds which yieldchloiine at an elevated tem-- perature, and compounds which yield bromine at an elevated temperature, said elevated temperature being considerably below the temperature at which an equivalent dehydrochlorination is possible in the absence of the said member.

8. A process according to claim 1 wherein the chlorinated hydrocarbon is ethylene dichloride and the resultant product is vinyl chloride.

9.Aprocessaccordingtoclaim1whcreinthe chlorinated hydrocarbon is symmetrical tetra- 11. A process according to claim 1 wherein the chloroethane and the resultant product is trlchlorinated hydrocarbon is propylene dichloride chloroethylene. and the resultant product is a mixture of mono- 10. A process according to claim 1 wherein the chloropropylenes.

chlorinated hydrocarbon is 1,1,2-trieh10roethane 5 MARTIN MUGDAN.

and the resultant product is a. mixture of asym- DEREK HAROLD RICHARD BARTON.

metrical and symmetrical dichloroethylenes. 

